Dicyanopyrazine compound, luminescent material, luminescence device using the same, and method for producing 2,5-dicyano-3,6-dihalogenopyrazine

ABSTRACT

A compound represented by formula (I) or formula (1I): 
     
       
         
         
             
             
         
       
         
         
           
             in formula (I), R 3  represents an electron donating group, R 4  represents a hydrogen atom, a substituted or unsubstituted aryl group or an electron donating group, L 3  represents a substituted or unsubstituted heteroarylene group or a substituted or unsubstituted arylene group, L 4  represents a single bond, a substituted or unsubstituted heteroarylene group or a substituted or unsubstituted arylene group, L 3  and L 4  may bond together to form a ring with the carbon atoms to which they are bonded, 
           
         
       
    
     
       
         
         
             
             
         
       
         
         
           
             in formula (II), R 5  represents an electron donating group, R 6  represents a hydrogen atom, a substituted or unsubstituted aryl group or an electron donating group, L 5  represents a substituted or unsubstituted heteroarylene group or a substituted or unsubstituted arylene group, L 6  represents a single bond, a substituted or unsubstituted heteroarylene group or a substituted or unsubstituted arylene group.

This is a Division of application Ser. No. 15/769,578, filed Apr. 19,2018, which in turn is a national phase of PCT/JP2016/083095, filed Nov.8, 2016, which claims the benefit of Japanese Patent Application No.2015-220371, filed Nov. 10, 2015, and Japanese Patent Application No.2015-242690, filed Dec. 11, 2015. The disclosure of the priorityapplications is hereby incorporated by reference herein in its entirety.

TECHNICAL FIELD

The present invention relates to a dicyanopyrazine compound, aluminescent material, a luminescence device using the same, and a methodfor producing a 2,5-dicyano-3,6-dihalogenopyrazine.

BACKGROUND ART

Several compounds among the compounds containing a dicyanopyrazineskeleton having an electron donating group are useful as electrontransport materials, charge generating materials, optical recordingmaterials, photoelectric conversion materials, luminescent materials,and the like.

For example. Patent Document 1 discloses an organic solid fluorescentsubstance containing N, N, N′, N′-tetrakis(2-methylbenzyl)-2,5-diamino-3,6-pyrazinecarbonitrile crystalrepresented by formula (1), of which the maximum reflectance in avisible light region by a reflectance measurement of a post-dispersivespectroscopy is 100% or more.

Patent Document 2 discloses a film obtained by adding a compoundcontaining a quinoxaline skeleton represented by formula (3) or2,3-dicyanopyrazine skeleton represented by formula (4) to1,4,5,8,9,11-hexaazatriphenylene hexacarbonitrile represented by formula(2). The film seems to be usable for organic electronic devices such asorganic electroluminescence devices, organic thin film solar cells orthe like.

Patent Document 3 discloses an organic electroluminescence device havinga layer containing a dicyanopyrazine compound represented by formula (5)between an anode and cathode which are opposite to each other.

In formula (5), R¹ and R² each independently represent a heterocyclicgroup which may have a substituent or a hydrocarbon ring group which mayhave a substituent.)

Patent Document 4 discloses a compound represented by formula (6) or thelike. The compound seems to be used for electron transport materials,charge generating materials, optical recording materials, photoelectricconversion materials, and the like.

Patent Documents 5 and 6 disclose compounds represented by formula (7),Formula (8) and the like. These compounds seem to be usable forfunctional materials such as electroluminescence and wavelengthconversion material or the like.

Patent Document 7 discloses a luminescent material including a compoundin which a cyano pyridine as an electron attractive site and aheteroaryl group as an electron donating site are bonded.

There are various methods for producing a compound containing adicyanopyrazine skeleton having an electron donating group. In order toobtain a compound containing a dicyanopyrazine skeleton having anelectron donating group at a low cost and in a high yield, it isnecessary to investigate starting materials and intermediates. Variouscandidates for starting materials or intermediates are conceivable. Forexample, a pyrazine compound having an amino group and a cyano group,such as 6-aminopyrazine-2,3,5-tricarbonitrile,5,6-diaminopyrazine-2,3-dicarbonitrile,3,5-diaminopyrazine-2,6-dicarbonitrile,3,6-diaminopyrazine-2,5-dicarbonitrile or the like can be synthesizedfrom a diamino maleonitrile or a homolog thereof as a starting material(see Non-Patent Document 2, Patent Document 8, Patent Document 9, etc.).

As the pyrazine compound having an amino group and a halogeno group, forexample, 2-amino-6-chloropyrazine, 2-amino-5-chloropyrazine,2-amino-5-bromopyrazine and 2-amino-3,5-dibromopyrazine are commerciallyavailable and readily available. The 2-amino-bromopyrazines are likelyto be synthesized by a method of reacting 2-aminopyrazines having atleast one hydrogen atom in the pyrazine nucleus with bromine in thepresence of a dehydrobromide agent in a solvent (Patent Document 11).This bromination is a substitution reaction of hydrogen to bromine.

As the pyrazine compound having a cyano group and a bromo group, forexample, 2,5-dicyano-3,6-dibromopyrazine can be prepared from2-cyano-3-aminopyrazine in a 4-step reaction or from2-cyano-3-amino-6-bromopyrazine in 3-step reaction (Non-Patent Document1). 2-cyano-3-aminopyrazine can be obtained by a method described inNon-Patent Document 3. A multi-step reaction is required for thesynthesis of a pyrazine compound having a cyano group and a bromo group.

PRIOR ART LITERATURE Patent Documents

-   [Patent Document 1] Japanese Unexamined Patent Application    Publication No. 2007-204443-   [Patent Document 2] Japanese Unexamined Patent Application    Publication No. 2015-153864-   [Patent Document 3] Japanese Unexamined Patent Application    Publication No. 2001-261658-   [Patent Document 4] Japanese Unexamined Patent Application    Publication No. 2001-2661-   [Patent Document 5] Japanese Unexamined Patent Application    Publication No. Hei 5-32640-   [Patent Document 6] Japanese Unexamined Patent Application    Publication No. Hei 11-138974-   [Patent Document 7] Japanese Unexamined Patent Application    Publication No. 2015-172166-   [Patent Document 8] Japanese Unexamined Patent Application    Publication No. Sho 63-75909-   [Patent Document 9] WO 91/03469 A-   [Patent Document 10] WO 88/01264 A-   [Patent Document 11] Japanese Unexamined Patent Application    Publication No. 2001-89460

Non-Patent Document

-   Non-patent document 1: N. Sato et al., “Synthesis of    3,6-dibromopyrazine-2,5-dicarbonitrile”, Journal of Heterocyclic    Chemistry, Vol. 49, May 2012, 675--   Non-patent document 2: J. Org. Chem., Vol. 39, 1235-(1974)-   Non-patent document 3: Journal of Heterocyclic Chemistry, Vol. 26,    1989, 817-

DISCLOSURE OF INVENTION Problems to be Solved by the Invention

An object of the present invention is to provide a novel dicyanopyrazinecompound and a luminescent material, and to provide a luminescencedevice using the luminescent material.

Further, it has been discovered that when a compound containing adicyanopyrazine skeleton having a halogeno group, such as2,5-dicyano-3,6-dibromopyrazine, is reacted with a compound capable ofserving as an electron donating group, a compound containing adicyanopyrazine skeleton having an electron donating group can beobtained in an extremely high yield.

An object of the present invention is to provide a method for producinga 2,5-dicyano-3,6-dihalogenopyrazine, which is used in a method forproducing a compound containing a dicyanopyrazine skeleton having anelectron donating group, from an inexpensive starting material with lessreaction steps and in a high yield

Means for Solving the Problems

As a result of intensive studies to solve the above problems, thepresent invention including the following embodiments has beencompleted.

That is, the present invention includes the following embodiments.

[1] A compound represented by formula (1) or formula (II).

[In formula (I), R³ represents an electron donating group, R⁴ representsa hydrogen atom, a substituted or unsubstituted aryl group or anelectron donating group, L³ represents a substituted or unsubstitutedheteroarylene group or a substituted or unsubstituted arylene group, L⁴represents a single bond, a substituted or unsubstituted heteroarylenegroup or a substituted or unsubstituted arylene group. L³ and L⁴ maybond together to form a ring with the carbon atoms to which they arebonded.]

[In formula (II), R⁵ represents an electron donating group, R⁶represents a hydrogen atom, a substituted or unsubstituted aryl group oran electron donating group, L⁵ represents a substituted or unsubstitutedheteroarylene group or a substituted or unsubstituted arylene group, L⁶represents a single bond, a substituted or unsubstituted heteroarylenegroup or a substituted or unsubstituted arylene group.]

[2] The compound according to [1], wherein R³ and R⁵ are at least oneselected from the group consisting of the groups represented by formulas(d1) to (d7).

(In formulas (d1) to (d7), R represents a substituent, a and b eachindependently represent a number of R in the parentheses and are aninteger of 0 to 4. c represents a number of R in the parentheses and isan integer of 0 to 2. d represents a number of R in the parentheses andis an integer of 0 to 5. When there are a plurality of R, they may bethe same substituents or different substituents. Two adjacent Rs maybond together to form a ring with the carbon atoms to which Rs arebonded. * represents a bonding site.)

[3] The compound according to [1] or [2], wherein R⁴ and R⁶ are at leastone selected from the group consisting of the groups represented byformulas (d1) to (d7).[4] The compound according to [1], [2] or [3], wherein L³, L⁴, L⁵ and L⁶are each independently a substituted or unsubstituted arylene group.[5] A luminescent material comprising the compound defined in any one of[1] to [4].[6] A luminescence device comprising the luminescent material defined inthe above [5].[7] A method for producing a 2,5-dicyano-3,6-dihalogenopyrazine (formula(11)), including

reacting (2E)-2,3-diamino-3-(substituted sulfanyl)-2-propenenitrile in asolvent in the presence of oxygen under acidic conditions to obtain2,5-dicyano-3,6-diaminopyrazine; and

subjecting the 2,5-dicyano-3,6-diaminopyrazine (formula (10)) to ahalogenation reaction in a solvent in the presence of nitrous acid ornitrite.

In formula (11), X represents a halogen atom.

[8] The method according to [7], wherein the(2E)-2,3-diamino-3-(substituted sulfanyl)-2-propenenitrile is a compoundrepresented by formula (9).

(In formula (9), R represents a substituted or unsubstituted aryl group,a substituted or unsubstituted alkyl group, a substituted orunsubstituted aralkyl group, or a substituted or unsubstituted alkenylgroup.)

[9] A method for producing a 2,5-dicyano-3,6-dihalogenopyrazineincluding subjecting a 2,5-dicyano-3,6-diaminopyrazine to a halogenationreaction in a solvent in the presence of nitrous acid or nitrite.[10] The method according to any one of [7] to [9], wherein atemperature during the halogenation reaction is 30 to 60° C.

Effects of the Invention

The dicyanopyrazine compound according to the present invention isuseful as a luminescent material. Some of the luminescent materialsaccording to the present invention emits delayed fluorescence. Theluminescence device including the luminescent material according to thepresent invention can provide excellent luminescence efficiency.

Further, according to the production method of the present invention, a2,5-dicyano-3,6-dihalogenopyrazine can be produced from an inexpensivestarting material with less reaction steps and in a high yield.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an absorption/emission spectrum of Ac-CNP toluene solutionA, Ac-CNP organic photoluminescence device B and Ac-CNP organicphotoluminescence device.

FIG. 2 shows a transient decay curve of Ac-CNP organic photoluminescencedevice C.

FIG. 3 shows a film configuration of Ac-CNP organic electroluminescencedevice.

FIG. 4 shows a light emission spectrum of Ac-CNP organicelectroluminescence device.

FIG. 5 shows a voltage-current density-light emission intensitycharacteristic of Ac-CNP organic electroluminescence device.

FIG. 6 shows a current density-external quantum efficiencycharacteristic of Ac-CNP organic electroluminescence device.

FIG. 7 shows a transient decay curve of Px-CNP organic photoluminescencedevice C.

FIG. 8 shows a film configuration of Px-CNP organic electroluminescencedevice.

FIG. 9 shows a light emission spectrum of Px-CNP organicelectroluminescence device.

FIG. 10 shows a voltage-current density-emission intensitycharacteristic of Px-CNP organic electroluminescence device.

FIG. 11 shows a current density-external quantum efficiencycharacteristic of Px-CNP organic electroluminescence device.

FIG. 12 shows a transient decay curve of BCz-CNP organicphotoluminescence device C.

FIG. 13 shows a film configuration of a BCz-CNP organicelectroluminescence device.

FIG. 14 shows an absorption/emission spectrum of PCz-DCP organicphotoluminescence device B and PCz-DCP organic photoluminescence deviceC.

FIG. 15 shows a transient decay curve of PCz-DCP organicphotoluminescence device C.

FIG. 16 shows a film configuration of a PCz-DCP organicelectroluminescence device (Device B).

FIG. 17 shows a film configuration of a PCz-DCP organicelectroluminescence device (Device A).

FIG. 18 shows a light emission spectrum of PCz-DCP organicelectroluminescence devices (Device B and Device A).

FIG. 19 shows a voltage-current density-emission intensitycharacteristic of PCz-DCP organic electroluminescence devices (Device Band Device A).

FIG. 20 shows a current density-external quantum efficiencycharacteristic of PCz-DCP organic electroluminescence devices (Device Band Device A).

FIG. 21 shows a transient decay curve of PAc-DCP organicphotoluminescence device C.

FIG. 22 shows a film configuration of a PAc-DCP organicelectroluminescence device (Device B).

FIG. 23 shows a film configuration of a PAc-DCP organicelectroluminescence device (Device A).

FIG. 24 shows light emission spectrum of PAc-DCP organicelectroluminescence devices (Device B and Device A).

FIG. 25 is shows a voltage-current density-emission intensitycharacteristic of PAc-DCP organic electroluminescence devices (Device Band Device A).

FIG. 26 shows current density-external quantum efficiency characteristicof PAc-DCP organic electroluminescence devices (Device B and Device A).

BEST MODE FOR CARRYING OUT THE INVENTION

The dicyanopyrazine compound of the present invention is a compoundrepresented by formula (I) or formula (II).

[in formula (I), R³ represents an electron donating group, R⁴ representsa hydrogen atom, a substituted or unsubstituted aryl group or anelectron donating group, L³ represents a substituted or unsubstitutedheteroarylene group or a substituted or unsubstituted arylene group, L⁴represents a single bond, a substituted or unsubstituted heteroarylenegroup or a substituted or unsubstituted arylene group. L³ and L⁴ maybond together to form a ring with the carbon atoms to which they arebonded.]

[in formula (II), R⁵ represents an electron donating group, R⁶represents a hydrogen atom, a substituted or unsubstituted aryl group,or an electron donating group, L⁵ represents a substituted orunsubstituted heteroarylene group, or a substituted or unsubstitutedarylene group, L⁶ represents a single bond, a substituted orunsubstituted heteroarylene group, or a substituted or unsubstitutedarylene group.]

In the present invention, the term “unsubstituted” means that the groupis solely formed of a group serving as a mother nucleus. When it isdescribed only by a name of a group serving as a mother nucleus, itmeans “unsubstituted” unless otherwise stated.

On the other hand, the term “substituted” means that at least one ofhydrogen atoms of a mother nucleus are substituted with a group having astructure same as or different from the mother nucleus. Accordingly, the“substituent” is another group bonded to the group serving as a mothernucleus. The number of substituents may be one, or two or more. Two ormore substituents may be the same or different.

The “substituent” is not particularly limited as long as it ischemically acceptable and has the effects of the present invention.

Specific examples of the “substituent” include the following groups.

A halogeno group such as a fluoro group, chloro group, bromo group, iodogroup or the like;

A C1-6 alkyl group such as a methyl group, ethyl group, n-propyl group,i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butylgroup, n-pentyl group, n-hexyl group or the like;

A C2-6 alkenyl group such as a vinyl group, 1-propenyl group, 2-propenylgroup, 1-butenyl group, 2-butenyl group, 3-butenyl group,1-methyl-2-propenyl group, 2-methyl-2-propenyl group, I-pentenyl group,2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenylgroup, 2-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group,3-hexenyl group, 4-hexenyl group, 5-hexenyl group or the like;

A C2-6 alkynyl group such as an ethynyl group, 1-propynyl group,2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group,1-methyl-2-propynyl group, 2-methyl-3-butynyl group, 1-pentynyl group,2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-2-butynylgroup, 2-methyl-3-pentynyl group, 1-hexynyl group,1,1-dimethyl-2-butynyl group or the like;

A C3-8 cycloalkyl group such as a cyclopropyl group, cyclobutyl group,cyclopentyl group, cyclohexyl group, cycloheptyl group, cubanyl group orthe like;

A C3-8 cycloalkenyl group such as a 2-cyclopropenyl group,2-cyclopentenyl group, 3-cyclohexenyl group, 4-cyclooctenyl group or thelike;

A C6-10 aryl group such as a phenyl group, naphthyl group or the like;

A 5-membered heteroaryl group such as a pyrrolyl group, furyl group,thienyl group, imidazolyl group, pyrazolyl group, oxazolyl group,isoxazolyl group, thiazolyl group, isothiazolyl group, triazolyl group,oxadiazolyl group, thiadiazolyl group, tetrazolyl group or the like;

A 6-membered heteroaryl group such as a pyridyl group, pyrazinyl group,pyrimidinyl group, pyridazinyl group, triazinyl group or the like;

A fused ring of heteroaryl group such as an indolyl group, benzofurylgroup, benzothienyl group, benzimidazolyl group, benzoxazolyl group,benzothiazolyl group, quinolyl group, isoquinolyl group, quinoxalinylgroup or the like;

A cyclic ether group such as an oxiranyl group, tetrahydrofuryl group,dioxolanyl group, dioxolanyl group or the like;

A cyclic amino group such as an aziridinyl group, pyrrolidinyl group,piperidyl group, piperazinyl group, morpholinyl group or the like;

A hydroxyl group; An oxo group;

A C1-6 alkoxy group such as a methoxy group, ethoxy group, n-propoxygroup, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group,t-butoxy group;

A C2-6 alkenyloxy group such as a vinyloxy group, allyloxy group,propenyloxy group, butenyloxy group or the like;

A C2-6 alkynyloxy group such as an ethynyloxy group, propargyloxy groupor the like;

A C6-10 aryloxy group such as a phenoxy group, naphthoxy group or thelike;

A 5- to 6-membered heteroaryloxy group such as a thiazolyloxy group,pyridyloxy group or the like;

A carboxyl group;

A formyl group; A C1-6 alkylcarbonyl group such as an acetyl group,propionyl group or the like;

A formyloxy group; A C1-6 alkylcarbonyloxy group such as an acetyloxygroup, propionyloxy group or the like;

A C1-6 alkoxycarbonyl group such as a methoxycarbonyl group,ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group,n-butoxycarbonyl group, t-butoxycarbonyl group or the like;

A C1-6 haloalkyl group such as a chloromethyl group, chloroethyl group,trifluoromethyl group, 1,2-dichloro-n-propyl group, 1-fluoro-n-butylgroup, perfluoro-n-pentyl group or the like;

A C2-6 haloalkenyl group such as 2-chloro-1-propenyl group,2-fluoro-1-butenyl group or the like;

A C2-6 haloalkynyl group such as a 4,4-dichloro-1-butynyl group,4-fluoro-1-pentynyl group, 5-bromo-2-pentynyl group or the like;

A C3-6 halocycloalkyl group such as a 3,3-difluorocyclobutyl group orthe like;

A C1-6 haloalkoxy group such as a 2-chloro-n-propoxy group,2,3-dichlorobutoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxygroup or the like;

A C2-6 haloalkenyloxy group such as a 2-chloropropenyloxy group,3-bromobutenyloxy group or the like;

A C1-6 haloalkylcarbonyl group such as a chloroacetyl group,trifluoroacetyl group, trichloroacetyl group or the like;

A cyano group; A nitro group; an amino group;

A C1-6 alkylamino group such as a methylamino group, dimethylaminogroup, diethylamino group or the like;

A C6-10 arylamino group such as an anilino group, naphthylamino group orthe like;

A formylamino group; A C1-6 alkylcarbonylamino group such as anacetylamino group, propanoylamino group, butyrylamino group,i-propylcarbonylamino group or the like;

A C1-6 alkoxycarbonylamino group such as a methoxycarbonylamino group,ethoxycarbonylamino group, n-propoxycarbonylamino group,i-propoxycarbonylamino group or the like;

A C1-6 alkylsulfoxyimino group such as an S,S-dimethylsulfoxyimino groupor the like;

An aminocarbonyl group;

A C1-6 alkylaminocarbonyl group such as a methylaminocarbonyl group,dimethylaminocarbonyl group, ethylaminocarbonyl group,i-propylaminocarbonyl group or the like;

An imino C1-6 alkyl group such as an iminomethyl group, (1-imino) ethylgroup, (1-imino)-n-propyl group or the like;

A hydroxyimino C1-6 alkyl group such as a hydroxyiminomethyl group,(1-hydroxyimino) ethyl group, (1-hydroxyimino) propyl group or the like;

A C1-6 alkoxyimino C1-6 alkyl group such as a methoxyiminomethyl group,(1-methoxyimino) ethyl group or the like;

A mercapto group;

A C1-6 alkylthio group such as a methylthio group, ethylthio group,n-propylthio group, i-propylthio group, n-butylthio group, i-butylthiogroup, s-butylthio group, t-butylthio group or the like;

A C1-6 haloalkylthio group such as a trifluoromethylthio group,2,2,2-trifluoroethylthio group or the like;

A C2-6 alkenylthio group such as a vinylthio group, allylthio group orthe like;

A C2-6 alkynylthio group such as an ethynylthio group, propargylthiogroup or the like;

A C1-6 alkylsulfinyl group such as a methylsulfinyl group, ethylsulfinylgroup, t-butylsulfinyl group or the like;

A C1-6 haloalkylsulfinyl group such as a trifluoromethylsulfinyl group,2,2,2-trifluoroethylsulfinyl group or the like;

A C2-6 alkenylsulfinyl group such as an allylsulfinyl group or the like;

A C2-6 alkynylsulfinyl group such as a propargylsulfinyl group or thelike;

A C1-6 alkylsulfonyl group such as a methylsulfonyl group, ethylsulfonylgroup, t-butylsulfonyl group or the like;

A C1-6 haloalkylsulfonyl group such as a trifluoromethylsulfonyl group,2,2,2-trifluoroethylsulfonyl group or the like;

A C2-6 alkenylsulfonyl group such as an allylsulfonyl group or the like.

A C2-6 alkynylsulfonyl group such as a propargylsulfonyl group or thelike;

A tri C1-6 alkylsilyl group such as a trimethylsilyl group,triethylsilyl group, t-butyldimethylsilyl group or the like;

A tri C6-10 arylsilyl group such as a triphenylsilyl group or the like;

In addition, any hydrogen atom in the “substituent” may be substitutedwith a group having a structure different from the “substituent”.

The term “C1-6” or the like means that the number of carbon atoms in thegroup serving as a mother nucleus is 1 to 6. The number of carbon atomsdoes not include the number of carbon atoms present in the substituents.For example, an ethoxybutyl group is classified as a C2 alkoxy C4 alkylgroup because the group serving as a mother nucleus is butyl group andthe substituent is ethoxy group.

The electron donating group for R³, R⁴, R⁵ or R⁶ in formula (I) orformula (II) is an atom or atomic group having a property of donating anelectron to the pyrazine ring. The Hammett's σ_(p) value of the electrondonating group is preferably less than 0. The Hammett's σ_(p) valuequantified the influence of the substituent on the reaction rate orequilibrium of the para-substituted benzene derivative. Specifically,the Hammett's σ_(p) value is a value defined by one of formulas (h1) and(h2).

Log(k/k0)=ρ*σ_(p)  (h1)

Log(K/K0)=ρ*σ_(p)  (h2)

k is a reaction rate constant of an unsubstituted benzene derivative, k₀is a reaction rate constant of a substituted benzene derivative, K is anequilibrium constant of an unsubstituted benzene derivative, K₀ is anequilibrium constant of a substituted benzene derivative, ρ is areaction constant determined by reaction types and conditions. For adetailed explanation of Hammett's σ_(p) value and the value of eachsubstituent, J. A. Dean ed., “Lange's Handbook of Chemistry 13thEdition”, 1985, 3-132 to 3-137, McGrow-Hill can be referred.

Examples of the electron donating group for R³, R⁴, R⁵ or R⁶ includethose groups containing a hetero atom and having a Hammett's σ_(p) valueof less than 0. Examples of the hetero atom include a nitrogen atom, anoxygen atom, a sulfur atom, a silicon atom, a phosphorus atom and thelike. A preferred electron donating group is a group having a bond atthe hetero atom or a group having a structure in which at least one ofthe hetero atoms is bonded to an sp² carbon atom so that a π conjugationincluding the sp² carbon atom extends to the pyrazine ring.

Examples of the group having a bond at the hetero atom include asubstituted or unsubstituted diarylamino group, a substituted orunsubstituted dialkylamino group, a substituted or unsubstitutedalkylarylamino group, a substituted or unsubstituted cyclic amino group,a substituted or unsubstituted aryloxy group, a substituted orunsubstituted alkyloxy group, a substituted or unsubstituted arylthiogroup, a substituted or unsubstituted alkylthio group, a substituted orunsubstituted triarylsilyl group, a substituted or unsubstitutedalkyldiarylsilyl group, a substituted or unsubstituted dialkylarylsilylgroup, a substituted or unsubstituted trialkylsilyl group, a substitutedor unsubstituted cyclic silyl group, a substituted or unsubstituteddiarylphosphino group, a substituted or unsubstituted dialkylphosphinogroup, a substituted or unsubstituted cyclic phosphino group, and thelike.

The group having a structure in which at least one of the hetero atomsis bonded to an sp² carbon atom so that a π conjugation including thesp² carbon atom extends to the pyrazine ring includes an aryl groupsubstituted with a group having a bond at the hetero atom, a heteroarylgroup substituted by a group having a bond at the hetero atom, an arylgroup substituted by a group having a structure in which a hetero atomis bonded to an sp² carbon atom and having a structure in which a πconjugation including the sp² carbon atom extends to the pyrazine ringvia the aryl group, a heteroaryl group substituted by a group having astructure in which a heteroatom is bonded to an sp² carbon atom andhaving a structure in which a π conjugation including the sp² carbonatom extends to the pyrazine ring via the heteroaryl group, an alkenylgroup substituted by a group having a structure in which a hetero atomis bonded to an sp² carbon atom and having a structure in which a πconjugation including the sp² carbon atom extends to the pyrazine ringvia the alkenyl group, an alkynyl group substituted by a group having astructure in which a hetero atom is bonded to an sp² carbon atom andhaving a structure in which a π conjugation including the sp² carbonatom extends to the pyrazine ring via the alkynyl group, and the like.

Preferable examples of the electron donating group for R³, R⁴, R⁵ or R⁶include a group having a bond at a hetero atom, an aryl groupsubstituted by a group having a bond at a hetero atom, a heteroarylgroup substituted by a group having a bond at a hetero atom, an arylgroup substituted by a group having a structure in which a hetero atomis bonded to an sp² carbon atom and having a structure in which a πconjugation including the sp² carbon atom extends to the pyrazine ringvia the aryl group, a heteroaryl group substituted by a group having astructure in which a heteroatom is bonded to an sp² carbon atom andhaving a structure in which a π conjugation including the sp² carbonatom extends to the pyrazine ring via the heteroaryl group; and morepreferable examples include a group having a bond at a hetero atom, anaryl group substituted by a group having a bond at a hetero atom, and anaryl group substituted by a group having a structure in which aheteroatom is bonded to an sp² carbon atom and having a structure inwhich a π conjugation including the sp² carbon atom extends to thepyrazine ring via the aryl group.

The aryl group which is a constituent of the electron donating group maybe either monocyclic or polycyclic. In the polycyclic aryl group, aslong as at least one ring is an aromatic ring, the remaining rings maybe a saturated ring, an unsaturated ring or an aromatic ring. The numberof carbon atoms constituting the unsubstituted aryl group is preferablyfrom 6 to 40, more preferably from 6 to 20, even more preferably from 6to 14.

Examples of the unsubstituted aryl group include a phenyl group,1-naphthyl group, 2-naphthyl group, azulenyl group, indanyl group,tetralinyl group and the like.

Examples of the substituted aryl group include a 4-fluorophenyl group,4-chlorophenyl group, 2,4-dichlorophenyl group, 3,4-dichlorophenylgroup, 3,5-dichlorophenyl group, 2,6-difluorophenyl group,4-trifluoromethylphenyl group, 4-methoxyphenyl group,3,4-dimethoxyphenyl group, 3,4-methylenedioxyphenyl group,4-trifluoromethoxyphenyl group, 4-methoxy-1-naphthyl group and the like.

The heteroaryl group which is a constituent of the electron donatinggroup may be either monocyclic or polycyclic. In the polycyclicheteroaryl group, as long as at least one ring is a heteroaromatic ring,the remaining rings may be a saturated ring, an unsaturated ring or anaromatic ring. The number of atoms constituting the unsubstitutedheteroaryl group is preferably from 5 to 40, more preferably from 5 to20, even more preferably from 5 to 14.

Examples of the unsubstituted heteroaryl group include a 5-memberedheteroaryl group such as a pyrrolyl group, furyl group, thienyl group,imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group,thiazolyl group, isothiazolyl group, triazolyl group, oxadiazolyl group,thiadiazolyl group, tetrazolyl group or the like; a 6-memberedheteroaryl group such as a pyridyl group, pyrazinyl group, pyrimidinylgroup, pyridazinyl group, triazinyl group or the like; a fused ringheteroaryl group such as an indolyl group, benzofuryl group,benzothienyl group, benzimidazolyl group, benzoxazolyl group,benzothiazolyl group, quinolyl group, isoquinolyl group, quinoxalinylgroup or the like; and the like.

The alkenyl group which is a constituent of the electron donating grouphas at least one carbon-carbon double bond in the molecule. Examples ofthe alkenyl group include a vinyl group, 1-propenyl group, 2-propenylgroup, 1-butenyl group, 2-butenyl group, 3-butenyl group,1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group,2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenylgroup, 2-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group,3-hexenyl group, 4-hexenyl group, 5-hexenyl group and the like.

The alkynyl group which is a constituent of the electron donating grouphas at least one carbon-carbon triple bond in the molecule. Examples ofthe alkynyl group include an ethynyl group, 1-propynyl group, 2-propynylgroup, 1-butynyl group, 2-butynyl group, 3-butynyl group,1-methyl-2-propynyl group, 2-methyl-3-butynyl group, 1-pentynyl group,2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-2-butynylgroup, 2-methyl-3-pentynyl group, 1-hexynyl group,1,1-dimethyl-2-butynyl group and the like.

The electron donating group for R³, R⁴, R⁵ or R⁶ is preferably at leastone selected from the group consisting of the groups represented byformulas (d1) to (d7), and more preferably at least one selected fromthe group consisting of the groups represented by formulas (d2), (d3)and (d6).

(In formulas (d1) to (d7), R represents a substituent, a and b eachindependently represent a number of R in the parenthesis and are aninteger of 0 to 4, preferably 0 or 1, and more preferably 0. crepresents a number of R in the parentheses and is an integer from 0 to2, and preferably 0. d represents a number of R in the parentheses andis an integer of 0 to 5, and preferably 0. When there is a plurality ofR, they may be the same substituents or different substituents. Twoadjacent Rs may bond together to form a ring with the carbon atoms towhich Rs are bonded. * represents a bonding site.)

Preferable examples of R include a hydroxy group, halogeno group, C1-20alkyl group, C1-20 alkoxy group, C1-20 alkylthio group, C1-20 alkylsubstituted amino group, C6-40 aryl-substituted amino group, C6-40 arylgroup, 5- to 40-membered heteroaryl group, C2-10 alkenyl group, C2-10alkynyl group, C2-20 alkylamido group, C6-20 arylamide group and triC1-10 alkylsilyl group; and more preferable examples include a C1-20alkyl group, C1-20 alkoxy group, C1-20 alkylthio group, C1-20alkyl-substituted amino group, C6-40 aryl-substituted amino group, C6-40aryl group and 5- to 40-membered heteroaryl group; and even morepreferable examples include a C6-40 aryl group.

Examples of the ring formed by bonding two adjacent Rs include a benzenering, naphthalene ring, pyridine ring, pyridazine ring, pyrimidine ring,pyrazine ring, pyrrole ring, imidazole ring, pyrazole ring, imidazolinering, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring,cyclohexadiene ring, cyclohexene ring, cyclopentene ring,cycloheptatriene ring, cycloheptadiene ring, cycloheptene ring and thelike.

The substituted or unsubstituted aryl group for R⁴ or R⁶ may be eithermonocyclic or polycyclic. In the polycyclic aryl group, as long as atleast one ring is an aromatic ring, the remaining rings may be asaturated ring, an unsaturated ring or an aromatic ring. The number ofcarbon atoms constituting the unsubstituted aryl group is preferablyfrom 6 to 40, more preferably from 6 to 20, and even more preferablyfrom 6 to 14.

Examples of the unsubstituted aryl group include a phenyl group,1-naphthyl group, 2-naphthyl group, azulenyl group, indanyl group,tetralinyl group and the like.

Examples of the substituted aryl group include a 4-fluorophenyl group,4-chlorophenyl group, 2,4-dichlorophenyl group, 3,4-dichlorophenylgroup, 3,5-dichlorophenyl group, 2,6-difluorophenyl group,4-trifluoromethylphenyl group, 4-methoxyphenyl group,3,4-dimethoxyphenyl group, 3,4-methylenedioxyphenyl group,4-trifluoromethoxyphenyl group, 4-methoxy-1-naphthyl group and the like.

The substituted or unsubstituted arylene group for L³, L⁴, L⁵ or L⁶ maybe monocyclic or polycyclic. In the polycyclic arylene group, as long asat least one ring is an aromatic ring, the remaining rings may be asaturated ring, an unsaturated ring or an aromatic ring. The number ofcarbon atoms constituting the unsubstituted arylene group is preferablyfrom 6 to 40, more preferably from 6 to 20, and even more preferablyfrom 6 to 14.

Examples of the arylene group include a phenylene group, naphthylenegroup, azulenylene group, indanylene group, tetralinylene group and thelike, and among these examples, a phenylene group is particularlypreferable.

The substituted or unsubstituted heteroarylene group for L³, L⁴, L⁵ orL⁶ may be monocyclic or polycyclic. In the polycyclic heteroarylenegroup, as long as at least one ring is a heteroaromatic ring, theremaining rings may be a saturated ring, an unsaturated ring or anaromatic ring. The number of atoms constituting the unsubstitutedheteroarylene group is preferably from 5 to 40, more preferably from 5to 20, and even more preferably from 5 to 14.

Examples of the heteroarylene group include a 5-membered heteroarylenegroup such as a pyrrolylene group, furylene group, thienylene group,imidazolylene group, pyrazolylene group, oxazolylene group,isoxazolylene group, thiazolylene group, isothiazolylene group,triazolylene group, oxadiazolylene group, thiadiazolylene group,tetrazolylene group or the like; a 6-membered heteroarylene group suchas a pyridylene group, pyrazinylene group, pyrimidinylene group,pyridazinylene group, triazinylene group or the like; a fused ringheteroarylene group such as an indolylene group, benzofurylene group,benzothienylene group, benzimidazolylene group, benzoxazolylene group,benzothiazolylene group, quinolylene group, isoquinolylene group,quinoxalinylene group or the like; and the like.

Examples of the ring formed by bonding L³ and L⁴ include a benzene ring,naphthalene ring, pyridine ring, pyridazine ring, pyrimidine ring,pyrazine ring, pyrrole ring, imidazole ring, pyrazole ring, imidazolinering, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring,cyclohexadiene ring, cyclohexene ring, cyclopentene ring,cycloheptatriene ring, cycloheptadiene ring, cycloheptene ring and thelike.

Specific examples of the dicyanopyrazine compound of the presentinvention include the following compounds. However, these compounds aremerely examples, and the present invention is not limited to theseexemplified compounds (I-1) to (I-13) and (II-1) to (II-9).

The dicyanopyrazine compound of the present invention can be obtained byperforming known synthetic reactions (for example, coupling reaction,substitution reaction, etc.) in combination.

For example, the compound represented by formula (I) can be obtained byreacting a diacetyl compound with a diaminomaleonitrile as shown in thefollowing formula.

Example I-1

Diamino maleonitrile (0.88 g, 8.2 mmol), 1,2-bis (4-bromophenyl)ethane-1,2-dione (3.0 g, 8.2 mmol) and hydrochloric acid (36%, 1.5 g)were reacted in 60 ml of ethanol at 60° C. for 3 hours in a nitrogenatmosphere. After cooling to room temperature, the reaction product wasextracted with 100 ml of dichloromethane and 100 ml of water. Theseparated organic phase was dried over anhydrous magnesium sulfate andthen filtered and evaporated to obtain 5,6-bis (4-bromophenyl)pyrazine-2,3-dicarbonitrile (3.2 g, yield of 90%), which is a mauvesolid.

¹H NMR (500 MHz, CDCl₃, δ): 7.58 (dd, 4H), 7.46 (dd, 4H); MS (MALDI-TOF)m/z: [M]⁺ calcd for C₁₈H₈Br₂N₄, 437.91; found, 437.70.

A substituent such as an electron donating group or the like can beintroduced by a substitution reaction of a halogeno group on a benzenering, or the like.

Example I-2

5,6-bis (4-bromophenyl) pyrazine-2,3-dicarbonitrile (1.0 g, 2.3 mmol),9,9-dimethyl-9,10-dihydroacridine (1.05 g, 5.1 mmol), bis(tri-t-butylphosphine) palladium (0) (0.012 g, 0.023 mmol) and potassiumcarbonate (0.95 g, 6.9 mmol) were stirred in 30 ml of toluene, whilerefluxing under a nitrogen atmosphere for 72 hours. The resultingmixture was cooled to room temperature, filtered through celite, and thesolvent was removed under reduced pressure. Purification by silica gelcolumn chromatography was performed to obtain 5,6-bis(4-(9,9-dimethyl-9,10-dihydroacridin-10-yl)-phenyl)pyrazine-2,3-dicarbonitrile (0.60 g, 40%), which is an orange solid.

¹H NMR (500 MHz, CDCl₃, δ): 7.87 (dt, J=8.5 Hz, 2 Hz, 4H), 7.47-7.43 (m,8H), 6.97-6.90 (m, 8H), 6.35 (dd, J=7.6 Hz, 1.3 Hz, 4H), 1.66 (s, 12H);¹³C NMR (125 MHz, CDCl₃, δ): 154.77, 144.69, 140.35, 134.21, 132.3,131.42, 130.84, 130.16, 126.48, 125.28, 121.48, 114.64, 113.04, 36.18,30.66; MS (MALDI-TOF) m/z: [M] calcd for C₄₈H₃₆N₆, 696.30; found,696.49. Anal. calcd for C₄₈H₃₆N₆: C, 82.73; H, 5.21; N, 12.06. found: C,82.21; H, 5.16; N, 11.85.

Example I-3

5,6-bis (4-bromophenyl) pyrazine-2,3-dicarbonitrile (1.0 g, 2.3 mmol),10H-phenoxazine (0.92 g, 5.1 mmol), bis (tri-t-butylphosphine) palladium(0) (0.012 g, 0.023 mmol) and potassium carbonate (0.95 g, 6.9 mmol)were stirred in 30 mol of toluene, while refluxing under a nitrogenatmosphere for 72 hours. Purification by silica gel columnchromatography was performed to obtain 5,6-bis(4-(10H-phenoxazin-10-yl)-phenyl) pyrazine-2,3-dicarbonitrile (1.03 g,70%), which is a red solid.

¹H NMR (500 MHz, CDCl₃, δ): 7.82 (dt, J=8.5 Hz, 2 Hz, 4H), 7.45 (d,J=8.5 Hz, 4H), 6.75-7.71 (m, 4H), 6.70 (td, J=7.5 Hz, 1 Hz, 4H), 6.59(td, J=8.0 Hz, 1.5 Hz, 4H), 5.97 (dd, J=8.0 Hz, 1 Hz, 4H); ¹³C NMR (125MHz, CDCl₃, 6): 154.52, 144.15, 140.34, 134.21, 133.43, 132.48, 131.33,123.38, 122.15, 115.91, 113.24, 122.85; MS (MALDI-TOF) m/z: [M]⁺ calcdfor C₄₂H₂₄N₆O₂, 644.21. found, 644.43. Anal. calcd for C₄₂H₂₄N₆O₂: C,78.25; H, 3.75; N, 13.04; 0, 4.96. found: C, 78.33; H, 3.65; N, 13.13.

Example I-4

Phenylhydrazine (10.0 g, 92.5 mmol), α-tetralone (13.5 g, 92.5 mmol) andethanol (100 mL) were stirred at room temperature under a nitrogenatmosphere and then hydrochloric acid (35%, 15 mL) was added thereto.The resulting mixture was stirred at 60° C. under a nitrogen atmospherefor 3 hours. Then, the resulting mixture was cooled to room temperature,and solids were filtered. 6,11-dihydro-5H-benzo [a] carbazole (18.2 g,90%), which is a white solid was obtained.

¹H NMR (500 MHz, CDCl3): 8.20 (br s, 1H), 7.56 (d, J=8.0 Hz, 1H), 7.39(d, J=8.0 Hz, 1H), 7.34 (d, J=7.5 Hz, 1H), 7.28-7.25 (m, 2H), 7.20-7.15(m, 2H), 7.14 (td, J=8.0 Hz, 1.0 Hz, 1H), 3.09-2.97 (m, 4H). MS(MALDI-TOF): m/z 219.32 [M]; calcd 219.10.

6,11-dihydro-5H-benzo [a] carbazole (10.0 g, 45.6 mmol) and p-xylene(100 mL) were stirred at room temperature under a nitrogen atmosphere.Palladium (10 wt %, 0.49 g, 4.56 mmol) carried on carbon was slowlyadded thereto. The resulting mixture was refluxed for 24 hours under anitrogen atmosphere. The resulting product was cooled to roomtemperature, filtered through celite, and the solvent was removed underreduced pressure. The resulting product was then washed with methanol toobtain 11H-benzo [a] carbazole (8.92 g, 90%), which is a white solid.

¹H NMR (500 MHz, CDCl₃): 8.81 (br s, 1H), 8.16 (t, J=8.5 Hz, 3H), 8.03(d, J=8.0 Hz, 1H), 7.68 (d, J=8.0 Hz, 1H), 7.63 (td, J=6.7 Hz, 1.25 Hz,1H), 7.56 (td, J=8.0 Hz, 1.25 Hz, 1H), 7.46 (td, J=7.2 Hz, 1.25 Hz,1.1H), 7.33 (td, J=8.0 Hz, 1.25 Hz, 0.8H). MS (MALDI-TOF): m/z 217.57[M]⁺; calcd 217.09.

5,6-bis (4-bromophenyl) pyrazine-2,3-dicarbonitrile (1.0 g. 2.3 mmol),11H-benzo [a] carbazole (1.11 g, 5.1 mmol), bis (tri-t-butylphosphine)palladium (0) (0.012 g, 0.023 mmol) and potassium carbonate (0.95 g, 6.9mmol) were stirred in 30 ml of toluene, while refluxing for 72 hoursunder a nitrogen atmosphere. The resulting mixture was cooled to roomtemperature, filtered through celite, and the solvent was removed underreduced pressure. Purification by silica gel-column chromatography wasperformed to obtain 5,6-bis (4-(11H-benzo [a] carbazol-11-yl)-phenyl)pyrazine-2,3-dicarbonitrile (0.50 g, 31%), which is an orange solid.Anal. calcd for C₄₈H₃₆N₆: C, 84.25; H, 3.96; N, 11.79. found: C, 84.21;H, 3.96; N, 11.07.

Examples I-5

The compound represented by formula (I) can be obtained by reacting adiamino maleonitrile with a phenanthrene-9,10-dione compound as shown inthe following formula.

A substituent such as an electron donating group or the like can beintroduced by a substitution reaction of a halogeno group on a benzenering or the like.

Example I-6

Example I-7

Example I-8

Example II-1

The compound represented by formula (II) can be obtained by reacting2,5-dicyano-3,6-dibromopyrazine with a compound having an electrondonating group as shown in the following formula.2,5-dicyano-3,6-dibromopyrazine can be obtained by, for example, themethod described in Non-Patent Document 1 and the like.

Example II-2

Purification of these compounds can be carried out by purification bycolumn chromatography, adsorption purification with silica gel,activated carbon, activated clay or the like, extraction with a solvent,recrystallization or crystallization method or the like. The structureof the compound can be determined by comparing the spectra of IR, NMR,Mass etc. to known structural isomers.

The method for producing a 2,5-dicyano-3,6-dihalogenopyrazine of thepresent invention includes:

(1st Step) reacting (2E)-2,3-diamino-3-(substitutedsulfanyl)-2-propenenitrile in the presence of oxygen under acidicconditions to obtain

2,5-dicyano-3,6-diaminopyrazine,

(2nd Step) subjecting the 2,5-dicyano-3,6-diaminopyrazine to ahalogenation reaction in the presence of nitrous acid or nitrite in asolvent.

In the formula, X represents a halogen atom, R represents a substitutedor unsubstituted aryl group, a substituted or unsubstituted alkyl group,a substituted or unsubstituted aralkyl group, or a substituted orunsubstituted alkenyl group. R is preferably a substituted orunsubstituted aryl group, and more preferably a phenyl group.

(2E)-2,3-diamino-3-(substituted sulfanyl)-2-propenenitrile (for example,a compound represented by formula (9)) which is a raw material can beeasily synthesized by a method described in Patent Document 10 or thelike.

(2E)-2,3-diamino-3-(substituted sulfanyl)-2-propenenitrile may be in theform of an acidic salt in an acidic solution.

Therefore, the reaction in the first step can be carried out (a) bydissolving (2E)-2,3-diamino-3-(substituted sulfanyl)-2-propenenitrile inan acidic solution, or (b) by dissolving an acidic salt of(2E)-2,3-diamino-3-(substituted sulfanyl)-2-propenenitrile in a solvent.

The reaction (a) is usually carried out in the presence of an organicsolvent or a mixed type of an organic solvent and water, in the presenceof an acid for adjusting the pH or a buffer solution, while blowing airaccording to need, at around 0 to 30° C. for 1 to a few hour underatmospheric pressure.

Examples of the organic solvent include hydrocarbons such as a benzene,toluene, xylene or the like, nitriles such as an acetonitrile or thelike, halogenated hydrocarbons such as a chloroform and methylenechloride or the like, esters such as an ethyl acetate or the like,alcohols such as a methanol, ethanol or the like, ketones such as anacetone, methyl ethyl ketone or the like, ethers such as a diethylether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane (DME),dimethylformamide, dimethyl sulfoxide (DMSO), and the like. Theseorganic solvents may be used alone or in combination of two or more.

The pH, which is an index of acidity, is preferably 1 to 5, morepreferably 2 to 4. For adjusting the pH, although any acid such as aninorganic acid or organic acid can be used, it is preferable to usevarious buffers.

In addition, the reaction in the first step is considered to be anoxidative dimerization condensation reaction. Therefore, it is necessaryto make the system an oxidizing atmosphere. Normally, it is onlynecessary to bring it into contact with atmospheric oxygen, but it ispreferable that air, oxygen or the like is actively blown into thereaction system.

In the reaction (b), a solvent capable of dissolving the acidic salt ofthe compound represented by formula (1), for example, a polar solventsuch as an acetonitrile, alcohols, dimethylformamide, dimethylsulfoxideor the like, or a mixed solvent thereof can be used. These solvents maycontain water. Although the reaction can be carried out at roomtemperature for 2 to 12 hours, it is desirable to make the reactionsystem an oxidizing atmosphere by blowing air or the like as in thereaction (a).

Examples of the acidic salt of the compound represented by formula (1)include inorganic acid salts such as a hydrochloride, sulfate, nitrate,perchlorate or the like, organic acid salts such as ap-toluenesulfonate, oxalate, picrate, trifluoroacetate or the like, andthe like.

By the reaction of the first step, 2,5-dicyano-3,6-diaminopyrazine isproduced. After completion of the reaction in the first step,2,5-dicyano-3,6-diaminopyrazine can be isolated according to need bycarrying out usual post-treatments.

Examples of the nitrite used in the reaction in the second step includemetal nitrites such as a sodium nitrite, potassium nitrite or the like;nitrite esters such as an n-butyl nitrite, t-butyl nitrite, isobutylnitrite, amyl nitrite, isoamyl nitrite, hexyl nitrite, isoamyl nitriteor the like, and the like. From the viewpoint of purification, nitriteesters are preferable. Generally, it is said that diazotization of anamino group proceeds by the action of nitrous acid or nitrite to form adiazonium salt. Although the amount of nitrous acid or nitrite to beused is not particularly limited, it is preferably 2 mol or more, andmore preferably 2.5 to 5 mol, with respect to 1 mol of2,5-dicyano-3,6-diaminopyrazine.

Examples of the halogenating agent include tetrafluoroboric acid, copper(I) bromide, copper (II) bromide, copper (I) chloride, copper (II)chloride, potassium iodide and the like. The amount of the halogenatingagent to be used is not particularly limited as long as it is an amountsufficient for brominating two amino groups in2,5-dicyano-3,6-diaminopyrazine.

Examples of the reaction solvent include hydrocarbons such as a benzene,toluene, xylene or the like, nitriles such as an acetonitrile or thelike, halogenated hydrocarbons such as a chloroform, methylene chlorideor the like, esters such as an ethyl acetate or the like, alcohols suchas a methanol, ethanol or the like, ketones such as acetone, methylethyl ketone or the like, ethers such as a diethyl ether,tetrahydrofuran, dioxane, 1,2-dimethoxyethane (DME) or the like,dimethylformamide, dimethylsulfoxide (DMSO), and these solvents can bemixed to use.

In the reaction of the second step, 2,5-dicyano-3,6-diaminopyrazine maybe added to a solution containing a halogenating agent and nitrous acidor nitrite; or nitrite or nitrite may be added to a solution containing2,5-dicyano-3,6-diaminopyrazine and a halogenating agent; or otheraddition orders may be used. However, since it is easy to control theheat generation and foaming during the reaction, it is preferable to addnitrous acid or nitrite to a solution containing2,5-dicyano-3,6-diaminopyrazine and a halogenating agent to carry outthe reaction. The addition is preferably carried out slowly to suppresssudden heat generation or foaming.

Although the temperature during the reaction in the second step is notparticularly limited, it is preferably 10 to 80° C., more preferably 20to 70° C., and even more preferably 30 to 60° C. The reaction in thesecond step is almost complete when 2,5-dicyano-3,6-diaminopyrazine,halogenating agent, and nitrite or nitrite coexist in one reactionsystem, specifically at the end of the addition. If the reaction is keptat a high temperature even after completion of the reaction, the productmay decompose. Therefore, in order to suppress decomposition of theproduct after completion of the reaction, it is preferable to cool downto room temperature or lower.

By the reaction in the second step, 2,5-dicyano-3,6-dihalogenopyrazineis produced. After completion of the reaction in the second step,2,5-dicyano-3,6-dihalogenopyrazine can be isolated according to need bycarrying out usual post-treatments.

The compound of the present invention can be used as a luminescentmaterial. The luminescent material of the present invention can providea luminescence device such as an organic photoluminescence device or anorganic electroluminescence device. Since the compound of the presentinvention has a function of assisting luminescence of other luminescentmaterials (host material), it can be doped with other luminescentmaterials to use.

The organic photoluminescence device of the present invention isprovided with a luminescent layer containing the luminescent material ofthe present invention on a substrate. The luminescent layer can beobtained by a coating method such as a spin coating or the like, aprinting method such as an inkjet printing method or the like, a vapordeposition method, or the like.

The organic electroluminescence device of the present invention includesan organic layer provided between an anode and a cathode. The term“organic layer” in the present invention means a layer located betweenan anode and a cathodes and substantially composed of an organicsubstance, and these layers may contain an inorganic substance within arange not impairing the performance of the luminescence device of thepresent invention.

As a structure of one embodiment of the organic electroluminescencedevice of the present invention, a structure in which an anode, a holeinjection layer, a hole transport layer, an electron blocking layer, aluminescent layer, a hole blocking layer, an electron transport layer,and a cathode are formed on a substrate in this order, and a structurehaving an electron injection layer between the electron transport layerand the cathode can be mentioned. In these multilayer structures, it ispossible to omit several layers of the organic layers. For example, itcan be a structure forming an anode, a hole transport layer, aluminescent layer, an electron transport layer, an electron injectionlayer and a cathode on a substrate in this order, or a structure formingan anode, a hole transport layer, a luminescent layer, an electrontransport layer and a cathode on a substrate in this order. Theluminescent material of the present invention may be doped in not onlythe luminescent layer but also the hole injection layer, the holetransport layer, the electron blocking layer, the hole blocking layer,the electron transport layer, or the electron injection layer.

The substrate serves as a support of the luminescence device, and asilicon plate, a quartz plate, a glass plate, a metal plate, a metalfoil, a resin film, a resin sheet or the like can be used. Inparticular, a glass plate and a transparent synthetic resin plate suchas polyester, polymethacrylate, polycarbonate, polysulfone or the likeare preferable. When a synthetic resin substrate is used, it isnecessary to pay attention to gas barrier properties. If the gas barrierproperty of the substrate is too low, the luminescence device may bedeteriorated by the outside air passing through the substrate.Therefore, it is preferable to provide a dense silicon oxide film or thelike on either side or both sides of the synthetic resin substrate toensure gas barrier properties.

The substrate is provided with an anode. In general, a material having ahigh work function is used for the anode. Examples of materials for theanode include metals such as aluminum, gold, silver, nickel, palladiumand platinum or the like; metal oxides such as indium oxide, tin oxide,ITO, zinc oxide, In₂O₃—ZnO, IGZO or the like; halogenated metals such ascopper iodide or the like, carbon black, conductive polymers such aspoly (3-methylthiophene), polypyrrole, polyaniline or the like, and thelike. In general, in many cases, the formation of the anode is performedby a sputtering method, a vacuum evaporation method, or the like.Further, when metal fine particles such as silver or the like, fineparticles such as copper iodide or the like, carbon black, conductivemetal oxide fine particles, conductive polymer fine powder and the likeare used, the anode can also be formed by dispersing them in anappropriate binder resin solution and coating it on a substrate.Furthermore, when a conductive polymer is used, it is also possible toform a thin film directly on the substrate by electropolymerization, orto form an anode by coating a conductive polymer on the substrate.

It is also possible to form the anode by laminating two or moredifferent substances. The thickness of the anode depends on atransparency to be required. In the case where a transparency isrequired, it is desirable that a transmittance of visible light isusually 60% or more, preferably 80% or more, and in this case, thethickness is usually from 10 to 1000 nm, preferably from 10 to 200 nm.If it can be opaque, the anode may be as thick as the substrate. Thesheet resistance of the anode is preferably several hundred Ω/□ or more.

As the hole injection layer provided as necessary, naphthalenediaminederivatives, starburst type triphenylamine derivatives, triphenylaminetrimers and tetramers such as arylamine compounds having three or moretriphenylamine structures connected by a single bond or by a divalentgroup not containing a hetero atom, acceptor heterocyclic compounds suchas a hexacyanoazatriphenylene and a coating type polymer material can beused in addition to porphyrin compounds typified by copperphthalocyanine. Other than the vapor deposition method, these materialscan be formed into thin films by a known method such as a spin coatingmethod or an ink jet method.

As the hole transport material used for the hole transport layerprovided as necessary, it is preferable that the hole injectionefficiency from the anode is high and that the injected holes can beefficiently transported. To that end, it is preferable that theionization potential is small, the transparency to visible light ishigh, the hole mobility is high, the stability is excellent, andimpurities which become traps are hardly generated at the time ofproduction or use. In addition to the above general requirement, whenconsidering the application for on-vehicle display, it is preferablethat the device has higher heat resistance. Therefore, a material havinga Tg value of 70° C. or higher is desirable.

Examples of the hole transport layer provided as necessary includetriazole derivatives, oxadiazole derivatives, imidazole derivatives,carbazole derivatives, indolocarbazole derivatives, polyarylalkanederivatives, pyrazoline derivatives, pyrazolone derivatives,phenylenediamine derivatives, arylamine derivatives, amino substitutedchalcone derivatives, oxazole derivatives, styryl anthracene derivative,fluorenone derivative, hydrazone derivatives, stilbene derivatives,silazane derivatives, aniline type copolymer, conductive polymeroligomer and the like. More specifically, a compound containing anm-carbazolylphenyl group, N, N′-diphenyl-N, N′-di (m-tolyl)-benzidine(hereinafter abbreviated as TPD), N, N′-diphenyl-N, N′-di(α-naphthyl)-benzidine (hereinafter abbreviated as NPD), benzidinederivatives such as N, N, N′, N′-tetrabiphenylyl benzidine or the like,1,1-bis [(di-4-tolylamino) phenyl]cyclohexane (hereinafter abbreviatedas TAPC), various triphenylamine trimers, tetramers, carbazolederivatives or the like, and the like. These can be used alone or incombination of two or more. The hole transport layer may be a film of asingle layer structure or a film of a laminate structure. In addition,as a hole injection/transport layer, a coating type polymer materialsuch as poly (3,4-ethylenedioxythiophene) (hereinafter abbreviated asPEDOT)/poly (styrene sulfonate) (hereinafter abbreviated as PSS) can beused. In addition to the vapor deposition method, these materials can beformed into thin films by a known method such as a spin coating methodor an ink jet method.

Further, in the hole injection layer or the hole transport layer, aP-doped tris bromophenylamine hexachloroantimony, a polymer compoundhaving the structure of PD in its partial structure, and the like can beused other than the materials commonly used for the above layer.Carbazole derivatives such as CBP TCTA, mCP and the like can be used asa host material of the hole injection/transport.

Compounds (hi1) to (hi7) which can be preferably used as the holeinjection material are listed below.

Compounds (ht1) to (ht38) which can be preferably used as the holetransport material are listed below.

As the electron blocking layer provided as necessary, compounds havingan electron blocking action, for example, carbazole derivatives such as4,4′,4″-tri (N-carbazolyl) triphenylamine (hereinafter abbreviated asTCTA), 9,9-bis [4-(carbazol-9-yl) phenyl] fluorene, 1,3-bis(carbazol-9-yl) benzene (hereinafter abbreviated as mCP), 2,2-bis(4-carbazol-9-ylphenyl) adamantane (hereinafter abbreviated as Ad-Cz) orthe like, compounds having a triphenylsilyl group typified by9-[4-(carbazol-9-yl) phenyl]-9-[4-(triphenylsilyl) phenyl]-9H-fluoreneand a triarylamine structure can be used. These can be used alone or incombination of two or more. The electron blocking layer may be a film ofa single layer structure or a film of a laminated structure. In additionto the vapor deposition method, these materials can be formed into thinfilms by a known method such as a spin coating method, an ink jet methodor the like.

Compounds (es1) to (es5) which can be preferably used as the electronblocking material are listed below.

The luminescent layer is a layer having a function of generatingexcitons by recombination of the holes and the electrons injected fromthe anode and the cathode respectively to emit light. The luminescentlayer may be formed of the luminescent material of the present inventionalone, or may be formed by doping the luminescent material of thepresent invention in a host material. Examples of the host materialinclude metal complexes of quinolinol derivatives such as a tris(8-hydroxyquinoline) aluminum (hereinafter abbreviated as Alq3), ananthracene derivative, a bisstyrylbenzene derivative, a pyrenederivative, an oxazole derivatives, a polyparaphenylene vinylenederivative, a compound having a bipyridyl group and an orthopterphenylstructure, mCP, a thiazole derivative, a benzimidazole derivative, apolydialkylfluorene derivative and the like. The luminescent layer maycontain a known dopant. As the dopant, a quinacridone, coumarin,rubrene, anthracene, perylene and derivatives thereof, benzopyranderivatives, rhodamine derivatives, aminostyryl derivatives and the likecan be mentioned. In addition, a phosphorescent luminescent body, forexample, a green phosphorescent luminescent body such as Ir(ppy)3 or thelike, a blue phosphorescent luminescent body such as FIrpic, Fir 6 orthe like, or a red phosphorescent luminescent body such as Btp2Ir (acac)or the like may be used. These can be used alone or in combination oftwo or more. The luminescent layer may be a film of a single layerstructure or a film of a laminated structure. In addition to the vapordeposition method, these materials can be formed into thin films by aknown method such as a spin coating method or an ink jet method.

In the case of using a host material, the lower limit of the amount ofthe luminescent material of the present invention that can be containedin the luminescent layer is preferably 0.1% by mass, more preferably 1%by mass, and the upper limit is preferably 50% by mass, more preferably20% by mass, and even more preferably 10% by mass.

Compounds (el1)-(el40) which can be preferably used as the host materialof the luminescent layer are listed below.

Examples of the hole blocking layer provided as necessary include acompound having a hole blocking action, for example, a compound having abipyridyl group and an orthopterphenyl structure, a phenanthrolinederivative such as a bathocuproin (hereinafter abbreviated as BCP), ametal complex of a quinolinol derivative such as an aluminum (III) bis(2-methyl-8-quinolinato)-4-phenylphenolate (hereinafter abbreviated toBAlq), various rare earth complexes, an oxazole derivative, a triazolederivative, a triazine derivative, and the like. These materials mayalso serve as the material of the electron transport layer. These can beused alone or in combination of two or more. The hole blocking layer maybe a film of a single layer structure or a film of a laminatedstructure. In addition to the vapor deposition method, these materialscan be formed into thin films by a known method such as a spin coatingmethod or an ink jet method.

Compounds (hs1) to (hs11) which can be preferably used as a holeblocking material are listed below.

As the electron transport layer provided as necessary, various metalcomplexes, triazole derivatives, triazine derivatives, oxadiazolederivatives, thiadiazole derivatives, carbodiimide derivatives,quinoxaline derivatives, phenanthroline derivatives, silole derivativesand the like can be used, in addition to metal complexes of quinolinolderivatives such as Alq3 and Balq. These can be used alone or incombination of two or more. The electron transport layer may be a filmof a single layer structure or a film of a laminated structure. Inaddition to the vapor deposition method, these materials can be formedinto thin films by a known method such as a spin coating method or anink jet method.

As the electron injection layer provided as necessary, although analkali metal salt such as lithium fluoride, cesium fluoride or the like,an alkaline earth metal salt such as magnesium fluoride or the like, ametal oxide such as aluminum oxide or the like can be used, it ispreferably to be omitted in the electron transport layer and thecathode.

In the electron injection layer or the electron transport layer, anN-doped metal such as N-doped cesium or the like may be used, inaddition to the material ordinarily used for the above described layers.

Compounds (et1) to (et30) that can be preferably used as the electrontransport materials are listed below.

Compounds (ei1) to (ei4) which can be preferably used as the electroninjecting material are listed below.

Compounds (st1) to (st5) which can be preferably used as the stabilizingmaterial are listed below.

For the cathode, a material with a small work function is generallyused. For example, sodium, sodium-potassium alloy, lithium, tin,magnesium, magnesium/copper mixture, magnesium/aluminum mixture,magnesium/indium mixture, aluminum/aluminum oxide mixture, indium,calcium, aluminum, silver, lithium/aluminum mixture, magnesium silveralloy, magnesium indium alloy, aluminum magnesium alloy and the like canbe used. By using a transparent conductive material, it is possible toobtain a transparent or translucent cathode. The thickness of thecathode is usually 10 to 5000 nm, preferably 50 to 200 nm. The sheetresistance of the cathode is preferably several hundred Ω/□ or more.

When a metal layer having a high work function and stable to theatmosphere, such as aluminum, silver, nickel, chromium, gold, platinumor the like, is further laminated thereon for the propose of protectingthe cathode made of a low work function metal, the stability of thedevice increases and thus it is preferable. Further, in order to improvecontact between the cathode and an adjacent organic layer (for example,an electron transport layer or an electron injection layer), a cathodeinterface layer may be provided between the cathode and the organiclayer. As a material used for the cathode interface layer, an aromaticdiamine compound, a quinacridone compound, a naphthacene derivative, anorganosilicon compound, an organophosphorus compound, a compound havingan N-phenylcarbazole skeleton, an N-vinylcarbazole polymer and the likecan be exemplified.

The luminescence device of the present invention can be applied toeither a single device, a device having a structure arranged in anarray, or a structure in which an anode and a cathode are arranged inX-Y matrix form.

The effect of the embodiment of the present invention will be describedbelow.

Organic photoluminescence devices and organic electroluminescencedevices were fabricated using the luminescent materials of the presentinvention, and light emission characteristics were evaluated.

Evaluation of the luminescent materials was performed using a sourcemeter (manufactured by Keithley Instruments Inc., 2400 series), asemiconductor parameter analyzer (manufactured by Agilent Technologies,E5273 A), an optical power meter measuring apparatus (manufactured byNewport KK, 1930C), an optical spectrometer (manufactured by OceanOptics Co., Ltd., USB 2000), a spectroradiometer (manufactured by TOPCONCORPORATION, SR-3), and a streak camera (manufactured by HamamatsuPhotonics KK, C4334 model).

Next, the present invention will be described in more detail by showingexamples. The present invention is not limited by these examples.Additions, omissions, substitutions, and other changes in theconfiguration are possible within a range not exceeding the significanceof the present invention.

Example 1

A toluene solution A (concentration: 10⁻⁴ mol/l) of Ac-CNP was preparedin a glove box under an argon atmosphere.

An organic photoluminescence device B including a thin film having athickness of 100 nm was obtained by depositing on a quartz substrateusing Ac-CNP as a vapor deposition source under a condition of vacuumdegree of 10⁻⁴ Pa or less.

An organic photoluminescence device C including a thin film havingAc-CNP concentration of 6.0 wt % and a thickness of 100 nm was obtainedby depositing on a quartz substrate using Ac-CNP and mCBP respectivelyas a vapor deposition source under a condition of 10⁻⁴ Pa or less.

For the toluene solution A, the organic photoluminescence device B andthe organic photoluminescence device C, the emission spectrum and theabsorption spectrum with 310 nm excitation light were measured. Theresults are shown in FIG. 1.

The photoluminescence quantum efficiency was 20.4% in the toluenesolution A with nitrogen bubbling, 9.3% in the toluene solution Awithout nitrogen bubbling, and 67.4% in the organic photoluminescencedevice C.

Transient decay curves of the organic photoluminescence device C at 5 K,50 K, 100 K, 150 K, 200 K, 250 K. and 300 K are shown in FIG. 2. In thistransient decay curve, a linear component (fluorescence component) isobserved at the beginning, but a component (delay component) deviatingfrom linearity is observed after several μ seconds. From this result, itcan be seen that Ac-CNP is a luminescent body (τ_(prompt)=45nanoseconds. τ_(delayed)=71 microseconds) including a delay component inaddition to the fluorescence component. In addition, it can be seen thatAc-CNP is a thermally activated delayed fluorescent material (TADF)because there is a change in the lifetime of the delay componentdepending on the temperature.

On a glass substrate on which an anode made of indium-tin oxide (ITO)and having a film thickness of 110 nm was formed, a hole transport layerwith a thickness of 40 nm, an electron blocking layer with a thicknessof 10 nm, a luminescent layer with a thickness of 20 nm, a hole blockinglayer with a thickness of 10 nm and an electron transport layer with athickness of 30 nm were laminated in this order by a vacuum vapordeposition method (5.0*10⁻⁴ Pa or less) (see FIG. 3).

α-NPD was used as the material of the hole transport layer.

mCP was used as the material of the electron blocking layer.

mCBP was used as the host material of the luminescent layer.

Ac-CNP was used as the doping material for the luminescent layer. Ac-CNPconcentration was set to 6.0% by weight.

PPF was used as the material of the hole blocking layer.

TPBi was used as the material for the electron transport layer.

Subsequently, a lithium fluoride film having a thickness of 0.8 nm andan aluminum film having a thickness of 80 nm were laminated in thisorder by a vacuum vapor deposition method to form a cathode, therebyobtaining an organic electroluminescence device.

The characteristics of the organic electroluminescence device weremeasured. FIG. 4 shows the emission spectrum. The emission spectrum wasin a range of about 500 nm to about 700 nm. FIG. 5 shows voltage-currentdensity-emission intensity characteristics. The data indicated by theleftward arrow indicates the voltage-current density characteristic, andthe data indicated by the rightward arrow indicates the voltage-emissionintensity characteristic. FIG. 6 shows the current density-externalquantum efficiency characteristic. The maximum external quantumefficiency was 13.3%. Since the theoretical limit value of the externalquantum efficiency of an organic electroluminescence device using afluorescent material is 5 to 7.5%, the organic electroluminescencedevice of the present invention obtained by using Ac-CNP realizes a highexternal quantum efficiency exceeding the theoretical limit.

Example 2

The characteristics were evaluated in the same manner as in Example 1except that Px-CNP was used instead of Ac-CNP. In the toluene solution,light emission in the visible region could not be observed. Thephotoluminescence quantum efficiency was 15.1% in the organicphotoluminescence device C. From the transient decay curve, it can beseen that Px-CNP is a luminescent body (τ_(prompt)=21 nanoseconds,τ_(delayed)=1.5 microseconds) including a delay component in addition tothe fluorescence component (see FIG. 7). Also, since there is a changein the lifetime of the delay component depending on the temperature, itcan be seen that Px-CNP is a thermally activated delayed fluorescentmaterial (TADF).

The characteristics of the organic electroluminescence device (FIG. 8)were measured. FIG. 9 shows the emission spectrum. As in Example 1, theemission spectrum was in the range of about 500 nm to about 700 nm. FIG.10 shows the voltage-current density-emission intensity characteristics.The data indicated by the leftward arrow indicates the voltage-currentdensity characteristic, and the data indicated by the rightward arrowindicates the voltage-emission intensity characteristic. FIG. 11 showsthe current density-external quantum efficiency characteristic. Themaximum external quantum efficiency was 3.0%.

Example 3

The characteristics were evaluated in the same manner as in Example 1except that BCz-CNP was used instead of Ac-CNP. The photoluminescencequantum efficiency was 15.6% in the toluene solution A with nitrogenbubbling, 10.8% in the toluene solution A without nitrogen bubbling, and54.7% in the organic photoluminescence device C. From the transientdecay curve, it can be seen that BCz-CNP is a luminescent body(τ_(prompt)=35 nanoseconds, τ_(delayed)=135 microseconds) including adelay component in addition to the fluorescence component (see FIG. 12).In addition, it can be seen that BCz-CNP is a thermally activateddelayed fluorescent material (TADF) because there is a change in thelifetime of the delay component depending on the temperature.

The characteristics of the organic electroluminescence device (FIG. 13)were measured. As in Example 1, the emission spectrum was in the rangeof about 500 nm to about 700 nm. The maximum external quantum efficiencywas 11.9° 0.

Example 4

An organic photoluminescence device B including a thin film having athickness of 100 nm was obtained by depositing on a quartz substrateunder a condition of vacuum degree of 10⁻⁴ Pa or less using PCz-DCP as avapor deposition source.

An organic photoluminescence device C including a thin film having aPCz-DCP concentration of 6.0% by weight and a thickness of 100 nm wasobtained by depositing on a quartz substrate under a condition of 10⁻⁴Pa or less using PCz-DCP and CBP respectively as a vapor depositionsource.

For the organic photoluminescence device B and the organicphotoluminescence device C, emission spectrum and absorption spectrumwith 310 nm excitation light were measured. The results are shown inFIG. 14.

The photoluminescence quantum efficiency was 36.5% in the organicphotoluminescence device C.

Transient decay curves of organic photoluminescence device C at 5 K, 50K, 100 K, 150 K, 200 K, 250 K, and 300 K are shown in FIG. 15. In thetransient decay curves, a linear component (fluorescence component) isobserved at the beginning, but a component (delay component) deviatingfrom linearity is observed after several microseconds. From this result,it can be seen that PCz-DCP is a luminescent body (T_(prompt)=28nanoseconds, τ_(delayed)=147 microseconds) containing a delay componentin addition to the fluorescence component. Also, since there is a changein the lifetime of the delay component depending on the temperature, itcan be seen that PCz-DCP is a thermally activated delayed fluorescentmaterial (TADF).

A 35 nm thick hole transport layer, a 15 nm thick luminescent layer, a10 nm thick hole blocking layer, and a 40 nm thick electron blockinglayer were laminated by a vacuum evaporation method (5.0×10⁻⁴ Pa orless) in this order on a glass substrate on which an anode made ofindium tin oxide (ITO) and having a film thickness of 110 nm was formed.

TAPC was used as the material for the hole transport layer.

CBP was used as the host material of the luminescent layer.

PCz-DCP was used as the doping material for the luminescent layer. ThePCz-DCP concentration was set to 6.0 wt %.

PPF was used as the material of the hole blocking layer.

B3PyPB was used as the material of the electron transport layer.

Subsequently, a lithium fluoride film having a thickness of 0.8 nm andan aluminum film having a thickness of 80 nm were laminated in thisorder by a vacuum vapor deposition method to form a cathode, therebyobtaining an organic electroluminescence device (Device B)(see FIG. 16).

Characteristics of the organic electroluminescence device (Device B)were measured. FIG. 18 shows the emission spectrum. As in Example 1, theemission spectrum was in the range of about 500 nm to about 700 nm. FIG.19 shows the voltage-current density-emission intensity characteristics.The data indicated by the leftward arrow indicates the voltage-currentdensity characteristic, and the data indicated by the rightward arrowindicates the voltage-emission intensity characteristic. FIG. 20 showsthe current density-external quantum efficiency characteristic. Themaximum external quantum efficiency was 7.8%.

Example 5

An organic electroluminescence device (Device A) was obtained in thesame manner as in Example 4 (see FIG. 17) except that 26 mCPy was usedinstead of CBP.

The characteristics of the organic electroluminescence device (Device A)were measured. FIG. 18 shows the emission spectrum. As in Example 1, theemission spectrum was in the range of about 500 nm to about 700 nm. FIG.19 shows the voltage-current density-emission intensity characteristics.The data indicated by the leftward arrow indicates the voltage-currentdensity characteristic, and the data indicated by the rightward arrowindicates the voltage-emission intensity characteristic. FIG. 20 showsthe current density-external quantum efficiency characteristic. Themaximum external quantum efficiency was 6.4%.

Example 6

The characteristics were evaluated in the same manner as in Example 4except that PAc-DCP was used instead of PCz-DCP. In the toluenesolution, light emission in the visible region could not be observed.The photoluminescence quantum efficiency was 31.9% in the organicphotoluminescence device C. From the transient decay curves, it can beseen that PAc-DCP is a luminescent body (τ_(prompt)=19 nanoseconds,τ_(delayed)=2.6 microseconds) containing a delay component in additionto the fluorescent component (FIG. 21). Also, since there is a change inthe lifetime of the delay component depending on the temperature, it canbe seen that PAc-DCP is a thermally activated delayed fluorescentmaterial (TADF).

The characteristics of the organic electroluminescence device (Device B:FIG. 22) were measured. FIG. 24 shows the emission spectrum. As inExample 1, the emission spectrum was in the range of about 500 nm toabout 700 nm. FIG. 25 shows voltage-current density-emission intensitycharacteristics. The data indicated by the leftward arrow indicates thevoltage-current density characteristic, and the data indicated by therightward arrow indicates the voltage-emission intensity characteristic.FIG. 26 shows the current density-external quantum efficiencycharacteristic. The maximum external quantum efficiency was 6.9%.

Example 7

An organic electroluminescence device (Device A) was obtained in thesame manner as in Example 6 except that α-NPD was used instead of TAPC,26 mCPy was used instead of CBP, and TPBi was used instead of B3PyPB(see FIG. 23).

The characteristics of the organic electroluminescence device (Device A)were measured. FIG. 24 shows the emission spectrum. As in Example 1, theemission spectrum was in the range of about 500 nm to about 700 nm. FIG.25 shows voltage-current density-emission intensity characteristics. Thedata indicated by the leftward arrow indicates the voltage-currentdensity characteristic, and the data indicated by the rightward arrowindicates the voltage-emission intensity characteristic. FIG. 26 showsthe current density-external quantum efficiency characteristic. Themaximum external quantum efficiency was 2.4%.

A luminescent material obtained by synthesizing a compound having2,3-dicyanopyrazine as a central skeleton (a compound represented byformula (I)) was found to have a high EL luminescence characteristic byevaluation based on TADF. Moreover, it was able to achieve an EQE valuefar higher than the theoretical limit value (5%) of the external quantumefficiency (EQE) of ordinary fluorescent molecules. The compoundrepresented by formula (1) is a very promising material as a TADFluminescent material.

A luminescent material obtained by synthesizing a compound representedby formula (II) having 2,5-dicyanopyrazine as a central skeleton wasfound to have a high EL luminescence characteristic by evaluation basedon TADF. In addition, it was able to achieve an EQE value higher thanthe theoretical limit value (5%) of the external quantum efficiency(EQE) of ordinary fluorescent molecules. The compound represented byformula (II) is a promising material as a TADF luminescent material.

Reference Example

400 mg of 2,3-diamino-3-(phenylthio) acrylonitrile was dissolved in 45ml of 1,2-dimethoxyethane, and the resulting solution was added to asolution containing 150 ml of 0.1 M citric acid-sodium citrate buffersolution (pH=3.0) and 150 ml of water. followed by leaving for 5 hoursat room temperature. Red-colored acicular crystals were filtered andwashed with 3 ml of n-hexane-ethyl acetate (3:1). 7.5 mg (yield 45%) of3,6-diamino-2,5-dicyanopyrazine was obtained.

¹³C-NMR (d₆-DMSO):149.730, 115.115, 113.251 ppm

Example 8

23.73 g (106.2 mmol) of copper (II) bromide and 10.95 g (118.0 mmol) oft-butyl nitrite were dissolved in 100 ml of dry acetonitrile. To theresulting solution, 3.40 g (21.2 mmol) of3,6-diamino-2,5-dicyanopyrazine was gradually added at 60° C. Foamingoccurred when 3,6-diamino-2,5-dicyanopyrazine was added. Aftercompletion of the addition, the mixture was reacted by stirring at 70°C. for 5 hours (reaction rate: 69.1%). The reaction solution was cooledto room temperature, poured into water, then extracted three times withchloroform, and separated into an organic phase and an aqueous phase.The organic phase was washed with water, then dried over anhydroussodium sulfate, filtered and concentrated. The crude product waspurified by silica gel chromatography and dried under vacuum to obtain2,5-dicyano-3,6-dibromopyrazine (4.1 g, yield 67.0 mol %).

¹³C-NMR (125 MHz, CDCl₃): δ 140.78, 134.25, 112.62. MS: m/z 287.01[M]⁺

Example 9

522 ml of acetonitrile (water content: about 250 ppm) was added to 40.0g (217.4 mmol) of 3,6-diamino-2,5-dicyanopyrazine and stirred to obtaina homogeneous solution. To this solution, 145.7 g (652.3 mmol) of copper(II) bromide was added. Then, while maintaining the solution at 40° C.,87.20 g (101 ml, 761.0 mmol) of t-butyl nitrite with a purity of 90% wasadded dropwise over 90 minutes. After completion of dropwise addition,reaction was carried out by stirring at 40° C. for 30 minutes (reactionrate (gross yield) of 80.1%). The reaction solution at 40° C. wasfiltered to remove insoluble matter. The filtrate was poured into waterto precipitate the solid at 10° C. and then filtered. The solid contentwas dissolved in toluene at 40° C. The resulting solution was filteredto remove insoluble matter. The filtrate was concentrated under reducedpressure at 55° C. N-hexane was added dropwise to the concentrate at 25°C., and after completion of the dropwise addition, it was cooled to 10°C. and filtered. Light yellow solid on the filter cloth was dried toobtain 45.34 g (yield (net yield) of 70.3 mol %, purity of 97%) of2,5-dicyano-3,6-dibromopyrazine.

Example 10

68 ml of dry acetonitrile was added to 2.25 g (14.1 mmol) of3,6-diamino-2,5-dicyanopyrazine, and stirred to obtain a homogeneoussolution. To this solution, 15.53 g (69.5 mmol) of copper (II) bromidewas added. Then, while the solution at 40° C., a mixture of 8.00 g (9.2ml, 69.8 mmol) of t-butyl nitrate with a purity of 90% and 9.2 ml of dryacetonitrile was added dropwise over 40 minutes. After completion ofdropwise addition, reaction was carried out by stirring at 40° C. for 4hours (reaction rate (gross yield) of 79.4%). The reaction solution at40° C. was filtered to remove insoluble matter. The filtrate was pouredinto water to precipitate the solid at 10° C. and then filtered. Thesolid content was dissolved in chloroform at 40° C. The resultingsolution was filtered to remove insoluble matter. The filtrate wasconcentrated under reduced pressure at 40° C. N-hexane was addeddropwise to the concentrate at 25° C., and after completion of thedropwise addition, it was cooled to 10° C. and filtered. Light yellowsolid on the filter cloth was dried to obtain 2.97 g (yield (net yield)of 72 mol %, purity of 98%) of 2,5-dicyano-3,6-dibromopyrazine.

Example 11

60 g of dry acetonitrile was added to 2.0 g (12.5 mmol) of3,6-diamino-2,5-dicyanopyrazine and stirred to obtain a homogeneoussolution. To this solution, 13.96 g (62.5 mmol) of copper (II) bromidewas added. Then, while maintaining the solution at 40° C., a mixedsolution of an n-butyl nitrite 7.21 g (8.1 ml, 62.9 mmol) with a purityof 90% and 8.1 ml of dry acetonitrile was added dropwise over 85minutes. After completion of dropwise addition, reaction was carried outby stirring at 40° C. for 2 hours (reaction rate (gross yield) of79.2%). The reaction solution at 40° C. was filtered to remove insolublematter. The filtrate was poured into water to precipitate the solid at10° C. and then filtered. The solid content was dissolved in chloroformat 40° C. The resulting solution was filtered to remove insolublematter. The filtrate was concentrated under reduced pressure at 40° C.N-hexane was added dropwise to the concentrate at 25° C., and aftercompletion of the dropwise addition, it was cooled to 10° C. andfiltered. Light yellow solid on the filter cloth was dried to obtain2.66 g (yield (net yield) of 69.9 mol %, purity of 94.6%) of2,5-dicyano-3,6-dibromopyrazine.

Example 12

Except that the mixed solution of 7.21 g of n-butyl nitrite with apurity of 90% and 8.1 ml of dry acetonitrile was replaced with a mixedsolution of 6.79 g (7.8 ml) of isobutyl nitrite with a purity of 95% and7.8 ml of dry acetonitrile, 2,5-dicyano-3,6-dibromopyrazine was obtainedin the same manner as in Example 4. The reaction rate was 79.5%, theyield was 70.0 mol %, and the purity was 95.4%.

Example 13

Except that the mixed solution of 7.21 g of n-butyl nitrite with apurity of 90% and 8.1 ml of dry acetonitrile was replace with a mixedsolution of 7.74 g (8.8 ml) of an isoamyl nitrite with a purity of 95%and 8.8 ml of a dry acetonitrile, and the dropwise addition time waschanged to 90 minutes, 2,5-dicyano-3,6-dibromopyrazine was obtained inthe same manner as in Example 4. The reaction rate was 78.8%, the yieldwas 69.6 mol %, and the purity was 95.3%.

Example 14

Except that the amount of 3,6-diamino-2,5-dicyanopyrazine was changed to2.0 g, the amount of copper (II) bromide was changed to 13.96 g, theamount of acetonitrile was changed to 60 ml, the amount of t-butylnitrite with a purity of 90% was changed to 7.13 g, the temperatureduring the reaction was changed to 30° C., the dropwise addition timewas changed to 30 minutes, and the stirring time after completion of thedropwise addition was changed to 4 hours,2,5-dicyano-3,6-dibromopyrazine was obtained in the same manner as inExample 4. The reaction rate was 76.4%.

Example 15

Except that the amount of 3,6-diamino-2,5-dicyanopyrazine was changed to2.0 g, the amount of copper (II) bromide was changed to 13.98 g, theamount of acetonitrile was changed to 60 ml, the amount of t-butylnitrite with a purity of 90% was changed to 7.13 g, the temperatureduring the reaction was changed to 60° C., the dropping time was changedto 20 minutes, and the stirring time after completion of the dropwiseaddition was changed to 3 hours, 2,5-dicyano-3,6-dibromopyrazine wasobtained in the same manner as in Example 4. The reaction rate was76.3%.

Example 16

Except that the amount of 3,6-diamino-2,5-dicyanopyrazine was changed to2.0 g, the amount of copper (II) bromide was changed to 13.96 g, theamount of acetonitrile was changed to 60 ml, the amount of t-butylnitrite with a purity of 90% was changed to 7.22 g, the stirring timeafter completion of the dropwise addition was changed to 3 hours,2,5-dicyano-3,6-dibromopyrazine was obtained in the same manner as inExample 1. The reaction rate was 72.4%.

Example 17

Except that the amount of 3,6-diamino-2,5-dicyanopyrazine was changed to2.0 g, the amount of copper (II) bromide was changed to 13.96 g, theamount of acetonitrile was changed to 60 ml, the amount of t-butylnitrite with a purity of 90% was changed to 7.22 g, and stirring aftercompletion of the dropwise addition was not carried out,2,5-dicyano-3,6-dibromopyrazine was obtained in the same manner as inExample 1. The reaction rate was 77.8%.

INDUSTRIAL APPLICABILITY

The present invention can provide a novel dicyanopyrazine compound and aluminescent material, and can provide a luminescence device using theluminescent material.

In addition, the present invention can provide2,5-dicyano-3,6-dihalogenopyrazine which is useful for producing acompound containing a dicyanopyrazine skeleton having an electrondonating group from an inexpensive starting material in a small reactionstep and in a high yield.

1. A compound represented by formula (II):

where: R¹ represents an electron donating group, R⁶ represents ahydrogen atom, a substituted or unsubstituted aryl group or an electrondonating group, L⁵ represents a substituted or unsubstitutedheteroarylene group or a substituted or unsubstituted arylene group, L⁶represents a single bond, a substituted or unsubstituted heteroarylenegroup or a substituted or unsubstituted arylene group.
 2. The compoundaccording to claim 1, wherein R⁵ is at least one selected from the groupconsisting of the groups represented by formulas (d1) to (d7):

where: R represents a substituent, a and b each independently representa number of R in the parentheses and are an integer of 0 to 4, crepresents a number of R in the parentheses and is an integer of 0 to 2,d represents a number of R in the parentheses and is an integer of 0 to5, and when there are a plurality of R, they may be the samesubstituents or different substituents, two adjacent Rs may bondtogether to form a ring with the carbon atoms to which Rs are bonded,and * represents a bonding site.
 3. The compound according to claim 1,wherein R⁶ is at least one selected from the group consisting of thegroups represented by formulas (d1) to (d7):

where: R represents a substituent, a and b each independently representa number of R in the parentheses and are an integer of 0 to 4, crepresents a number of R in the parentheses and is an integer of 0 to 2,d represents a number of R in the parentheses and is an integer of 0 to5, and when there are a plurality of R, they may be the samesubstituents or different substituents, two adjacent Rs may bondtogether to form a ring with the carbon atoms to which Rs are bonded,and * represents a bonding site.
 4. The compound according to claim 1,wherein L⁵ and L⁶ are each independently a substituted or unsubstitutedarylene group.
 5. A luminescent material comprising the compound definedin claim
 1. 6. A luminescence device comprising the luminescent materialdefined in claim 5.